| The polarity and rigidity of the chemically modified thiacalix[4]arenes have been greatly changed,and they have many properties that classical calixarenes do not possess.Due to the modulable geometry,size,charge state and oxygen-enrich nucleophilic surface of polyoxometalates,they can be used in the fields of catalysis,electrochemistry,materials and biology.In recent years,the design and synthesis of high dimensional(2D or 3D)POM-based inorganic-organic hybrids have been a research hot point.It has received plenty of attention that chemically modified thiacalix[4]arenes,as excellent multi-dentate organic ligands,have been used to construct inorganic-organic hybrids with POM.In this paper,a novel thiacalix[4]arene ligand modified by1-methyl-5-ethylenethiotetrazole(L)was successfully synthesized.Three POM-thiacalix[4]arene-based hybrids[Ni3L2(CH3OH)6(H2O)4][PMo12O40]2·3CH3OH·2H2O(1),[Ni3L2(CH3OH)6(H2O)4][Pw12O40]2·3CH3OH·2H2O(2)and[Ag3L(PMo12O40)](3)were synthesized by self-assembling of polyoxometalates,metal cations and L ligand.In the isomorphic hybrids of 1 and 2,Ni(II)cations are connected by L ligands to produce layered frameworks,and H bonds between the[PMo12O40]3-/[PW12O40]3-anion and L ligand link the layered structures to form 3D supramolecular architectures.Hybrid 3 exhibits 3D architecture.It is worth mentioning that one Ag ion and its symmetry-related atom form a metallic bond.L ligand was characterized by 1H NMR and IR spectra.The crystal structures of 1-3 were determined by single crystal X-ray diffraction analyses,and the compounds were characterized by TGA,IR spectra,elemental analysis and PXRD.In consideration of the[PMo12O40]3-units in hybrids 1 and 3,their catalytic activities for catalytic ODS reactions were studied.The results showed that 1 and 3 as efficient heterogeneous catalysts had excellent catalytic activity,and the catalytic effect could still achieve 99%and 98%after multiple cycles.In addition,since hybrids 1-3 contain POM,the electrochemical and photoelectrocatalytic properties of hybrids 1-3 were tested.The experimental results show that hybrids 1-3 have very obvious electrocatalytic effect for the oxidation of AA and the reduction of Na Br O3,and the semiconductor modified by hybrid 1has obvious photoelectrocatalytic effect for the degradation of tetracycline hydrochloride. |
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